Production of depolymerizates from polymers cross-linked by s (se, te) halides



United States Patent 3,296,203 PRODUCTION OF DEPOLYMERIZATES FROM POLYMERS CROSS-LINKED BY S(Se, Te) HA- LIDES Lev Akobjanoff, 2726 Hillegass Ave., Berkeley, Calif. 94705 No Drawing. Filed May 8, 1961, Ser. No. 108,276 15 Claims. (Cl. 260-48) This application is a continuation-in-part of my copending application Serial Number 721,081, filed March 13, 1958, now abandoned, which in turn is a continuationin-part of my application Serial Number 397,032, filed December 8, 1953, now abandoned, 'which in turn is a continuation-in-part of my application Serial Number 188,477, filed October 4, 1950, now abandoned, which in turn is a continuation-in-part of my application Serial Number 86,126, filed April 7, 1949, now abandoned.

This invention relates to the production of highly reactive organic poly-sulfo (Se, Te) halides by depolymerization of condensates already cross-linked by said halides of the sulfur family. Its essential feature is the use for the depolymerization of these halides in such proportions exceeding the requirements of exhaustive crosslinking of the condensate.

Condensates cross-linked by S(Se, Te) halides have been known for rubber and drying oils since the pioneering work of Henriquez (Chemiker Zeitung 17, 637 and 707 (1893)), Weber (Chemik.-Ztg. 18, 837 (1894)), Bernstein (Kolloid Zeitschrift 11, 185 (1912)), Le Blanc (Koll. Ztsch. 33, 168 (1923)), for polyalcohols and polyketones since the publications of Ellis (Chemistry of Synthetic Resins II, 1061 (1935)) and Stern (USP 1,218,713). The common feature of molecules undergoing cross-linking is the presence of two or more unsaturated constituents reactive with S(Se, Te) halides.

The reaction disclosed herein goes beyond the crosslinking explored by the above authors. Essential for its performance is the novel-treatment of organic molecules containing two or more unsaturated constituents such as: multiple bonds, oxygen linkages, nitrogen linkages with halides of sulfur, selenium and tellurium in amounts exceeding one half equivalent of halide per each equivalent of unsaturated constituents of the organic molecules.

(Prior to the reaction disclosed herein the organic molecules must be exhaustively cross-linked. This occurs automatically upon the addition of sulfur(Se, Te) halides by the below one half equivalent per equivalent of unsaturation portion of the halide regardless of whether the original organic substance is still monomeric or may have been subjected to condensation, polymerization, vulcanization, etc., of any extent up to but not beyond the exhaustive cross-linking.) V

In chemical symbols the reaction known to Henriquez and his followers can be represented, for instance by the "ice stages (a) through (c) of the following diagram, while the depolymerization is shown by stage (d) R R Ht} Hi M equivalent of HA (318201 2 7 per equivalent 0 H of unsaturation HO H L I l R Monomer with two unsaturated links Monomer with two unsaturated links HCl H501 Additional He equivalent R R H4301 HJJOI SzClrin excess of% R and R denote organic radicals H is hydrogen C is carbon S, element of the sulfur family Cl, a halogen unsaturated link i, conjugated or not The end-products of the depolymerization disclosed herein are essentially of the same consistency, softness, plasticity, viscosity as the original unsaturated molecules. However, chemically they have lost their unsaturation instability, gaining at the same time high reactivity due to the unilaterally grafted halides of the sulfur family; Thus, for instance, they quickly co-condensate with unsaturated molecules added subsequently to the product of depolymerization. This is illustrated by the stages (e) and (f) of the diagram.

Such physical and chemical properties are of practical value, for instance, in the manufacture of surface coattion of the unsaturation in the organic sub-stratum by said halides added in excess of the requirement of a total crosslinking (more than one half equivalent of halide per equivalent of unsaturation) can be demonstrated, e.g., by the evolution of the consistency in arachidonic acid. Upon the treatment of the latter with various amounts of sulfur chloride, the fluidity, viscosity, and hardness of the reaction products reflects the molecular size of arachidonic vulcanizates which are proportional to the numbers of bridges cross-linking the originally monomeric molecules. The molecules or arachidonic acid contain 5 or 6 double bonds and 60 grams of it corresponds to 1.1 equivalents of unsaturation, yielding with some 70 grams of S Cl (0.55 equilavent) the maximum of cross-linking (condensation), while larger amounts of sulfur chloride result in products of decreasing polymerity (viscosity), as obvious from Table I:

TABLE I.REACTIONS OF INCREASING AMOUNTS OF SULFUR CHLORIDE WITH ARAOHIDONIC ACID Grams of SgCh per 2632 40-64 72-100. 106-120.- 126-154.

60 grams of acid.

Characteristics of Pasty Brittle Hard" Elastic Plasticcondensates. liquid.

It is immaterial for the execution of this invention whether or not the depolymerization treatment is distinctly separated in time or space from the initial cross-linking reaction, since the sulfur(Se, Te) halide in excess of /2 equivalent may be added directly to the orginal unsaturated compound, as for instance, in treating a Z-6 body soybean oil with various amounts of SCl recorded in Table II:

TABLE IL-REACTIONS OF SULFUR DIOHLORIDE WITH VARIOUS AMOUNTS OF A Z-fi BODY SOYBEAN OIL DIS SOLVED IN BENZENE Grams of SO1 per 125 grams oioils 6.7 13.4 20.0 26.8 33.4 40.0 47 53.5 60 Time of gelation (minutes) w 36 1.5 2.5 65 270 420 800 w The reactivity of the depolymerized products is obvious from the following: A depolymerized sulfenyll chloride prepared by treating 100 grams of arachidonic acid (1.8 equivalents of unsaturation), dissolved in 200 ml. of carbon tetrachloride, with 220 grams of S Cl (0.7'5 equivalent in excess of the 0.9 equivalent required for the complete cross-linking), is a dark oil of medium viscosity, which reacts readily with unsaturated substances at room temperature by simple mixing, giving with:

Nature of resulting Added substance: product Methanol, ethanol, propanol,

butanol, amylol, hexanol Tough, plastic masses.

The attainment of the state of depolymerization can be ascertained by boiling a sample with water. Depolymerization yields lightly colored spongy masses evolving S whereas regularly cross-linked condensates are neutral to water.

This behaviour of depolymerized condensates is similar to that of organic monosulfenyl-chlon'des whose reactions with H O, NH aromatic bases, Na S, Na SO alkali hydroxides, ClCH COOH, C H OH, para cresol, trichlorophenol, naphtol, ethylene, acetone, esters, piperazine, have been studied by Conant (JACS 42, 585 1920)), Friedlander (Berichte 55B, 3969 (1922)), Standard Oil (USP 2,422,276)), Fuson (J. Org. Chem. 11, 469 (1946)). However, while the depolymerized molecules of this invention carry two or more sulfenyl(Se, Te) halide groups and may be used anew for cross-linking condensation, as shown above this is not possible for the singly sulfo(Se, Te)-halogenated compounds described by Conant, Friedlander, Standard Oil and Fuson, which at the most may yield dimers (as shown in the next paragraph).

The structure of the depolymerized products contains sulfenyMSe, Te) halides 'with end-standing reactive halogens which can be deduced by analogy from the following: By treating ethylene(H C=CH with sulfur chloride in equimolecular proportions (twice the amount of S CI which is required to produce the dimer Conant (JACS 42, 585 (1920)) and Fuson (J; Org. Chem. 11, 469 (1946)) obtained monomeric whose sulfenyl chloride (-S Cl) group reacts in the same way as unattached su'lfur chlorides (S01 S 01 do, the structures of which are known to be be Cl--SCl and ClSSCl (Stevenson and Beach, JACS 60, 2972 (1938)).

Unsaturated constituents reacting with S(Se, Te) hal-ides in terms of this invention are the structural elements which introduce into molecules the so-called pi-elec-. trons, binding forces resonating (moving) readily be-. tween atoms and promoting chemical reactivity (Glasstone Textbook of Physical Chemistry pp. and 582 (1946)). So that any of the following, if part of an organic molecule-will act as an unsaturated constituent responsible first for the cross-linking and then for the depolymerization of condensates: Multiple bonds (double and triple) in olefines, acetylenes, napthalenes, anthracenes, etc.; saturated side chains of branched aliphatic compounds ;oxygen links in acetals, alcohols, aldehydes, esters, carboxylic acids, ketones, phenols, etc.; nitrogen links in amines, amides, imines, etc.; metal-organic groups; metal oxides such Ag O, BaO, CaO, CdO, Cu O, CuO, HgO, MgO, MnO, MnO Na O, Na O NiO, P'bO, Pb O, SrO, ZnO; metalloids such as As, P (yellow and red), Si, Sb; metals such as Al, Bi, Cu, Fe, Hg, Sn, Zn; oxides, chlorides, sulfides like AlCl As O As S AS253, Bi O P01 Sb O ,CbCl

The organic molecules carrying these constituents may be straight chains, saturated or unsaturated chains, branched chains, cyclic, aromatic, mixed aromatic and aliphatic, heterocyclic, heterocyclic and aromatic, heterocyclic and aliphatic, or mixed aromatic, aliphatic, cyclic and heterocyclic.

The terms chalco-halide, S(Se, Te) halide, sulfur(Se, Te) halide applies to all halides of the sulfur family, for example, SBI'Z, SC12, SZBI'Z, sgclz, SC14, S212, S2132, 862012, 86 1313,), 861313;, S6014, TeCl TeBL; Others. Halides of other elements than S, Se and AlCl PO1 SiCl SnCl TiCl ZnCl otherwise known as powerful catalysts of polmerization, cannot be used for this kind of cross-linking and depolymerization.

Various unsaturated constituents may "be present in the original molecules as long as two or more of them per molecule are available for the reactions (see Table In).

Tc, for example i TABLE III.-POLY-SULFENYL-CHLORIDES RESULTING FROM REACTING 100 GRAMS OF VARIOUS UNSATURATED COM- POUNDS WITH AROMATIC SOLUTIONS OF SCI: AND SzCla Substance Cause of Unsaturation Amount of Chloride Nature of Sulfenyl Acetylaeetone (undiluted) Enolization 1 Over 32 gr. SClz Red-viscous liquid.

Butyl Rubber (5% aromatic solution Double brm (ls 16 gr. SC: Elastic, sticky.

Cyclicized Rubber 120 gr. SO12- Hard, reddish grey.

Glyrnl Over 600 gr. 5401:. Yellow wax.

Glycolethylether. Over 16 gr. SO12. Yellow paste.

Linoleic Acid (50% naphta solution) Over 32 gr. S1012 Brown paste.

Malonic Ester (undiluted) Over 32 gr. SO11- Viscous liquid.

Pale Crepe Rubber (5% aromat. solution 1 gr. S Hard, yellowish.

Phenylene Diamine (fine powder) Over 16 gr. SO1 Brown oil.

Resorcinol (fine powder) 64 gr. SO12 Brown viscous oil.

Saccharose (fine powder) Over 16 gr. SO12." Yellow viscous liquid. Soybean Oil (undiluted) 200 gr. S2012"- Viscous black oil.

Turpentine (undiluted) o 128 gr. SCl2 Yellow wax.

Urea (aromatic suspension) Resonance Over 16 gr. SC Yellow viscous liquid.

Urea (saturated water solution) d0 660 gr. S4012 (un uted) Yellow paste.

1 According to modern views the unsaturation of organic molecules may result in structural enolization, resonance, tautomerism."

The reacting substances may be employed each by itself or in combinations, for example oils with rubber, allyl monomers with alkyl-modified oils, etc.

Since the procedure described here requires the presence of condensable molecules and consists in reacting them with halides of the sulfur family in proportions exceeding the needs of total-cross-linking, it has nothing in common e.g. with: the making of viscous non-penetrating oils by thickening them with up to 7% S Cl the manufacturing of highly condensed rubber substitutes from the same oils with some 30% of sulfur chloride; the so-called coldv-ulcanization, where 1% or less of S Cl react with rubber, producing in it a state of elasticity; the perc-hloromethyl-mercaptan Cl CSCl (USP 2,197,781); the di-chloro-ethylsulfenyl-chloride CI CHS CI (USP 2,484,061); the work of Ca-lcott (USP 1,896,157), of Garvey (I. E. Ch. 29, 208 (1937)), of Herrmann (USP 1,627,157); the partly vulcanized butyl rubber of Sparks (USP 2,471,093).

Of all previous investigators Le Blank (Koll, Zeitschr. 33, 168 (1923)) has treated rubber with sufiicient amounts of S Cl to obtain a depolymerization of the total vulcanizate. However, he did not expect anything like a depolymerization to occur, and, due to unfavorable experimental conditions, he did not observe anything besides gelation of his 1% solutions, though, as shown below, rubber-sulfenyl-chloride solutions of higher concentrations than his remain permanently liquid.

Weber (The Chemistry of Rubber Manufacture, London (1926) p. 82) speaks of using an excess of sulfur chloride. However, he states clearly that his reaction products did not reach higher proportions of S and Cl than those of formula C H S Cl even when an excess of S CI was added. It has been known for a long time that the structure of this composition is that of a totally cross-linked condensate (which has no unilaterally bound sulfenyl groups). Apparently Weber did not leave the excessive sulfur chloride long enough in contact with the cross-linked rubber to produce a depolymerization in terms of this invention.

Snellings Improved Factice (USP 1,430,034) cannot contain depolymerizates in terms of this invention because otherwise the obtained product could not be used as substitute, i.e. compounded to rubber without immediate search ing (vulcanization during processing which renders the stock useless). Snelling seems to have treated linseed oil with sufiicient amounts of sulfur chloride to produce depolymerization, however, without allowing enough time for the reaction to take place. Neither did depolymerization occurin the rubber sulfur chloride of Bernstein (Koll. Zeitschr. 11, 185 (1912)), whose statement (p. 191b, paragraph below the table), that: On examining these analytical tables, one finds, that addition of S Cl from 65.85 to 658% on the used rubber, results in insoluble products, which deviate very little from the constant value: chlorine 17.4% and sulfur 15.7%, i.e. ratios of chlorine and sulfur close to the theoretical, is conclusive in this respect. This theoretical composition is indicated by him as C H S CI (p. 187a), which is nothing more than an exhaustively cross-linked condensate.

Becker (Rec. Trav. Chim. Pays Bas 54, 52 (1935)) treated butadiene and isoprene with sulfur chloride in excess of /2 equivalent per double bond, however, since he clearly shows, that the prepared products correspond to the structures:

as well as CH ClCHClCHClCH Cl, he did not produce depolymerized cross-links.

All previous investigators failed to show for the reaction of sulfur chlorides with molecules containing more than one double bond, that the produced condensation attains a maximum for very definite proportions of the reactants; that amounts of sulfur chlorides exceeding this ratio cause depolymerization, bringing about lower consistenciesz' chlorinated, hydrogenated or aliphatic. Combinations of various liquids may be employed in order to attain various reaction velocities and degrees of depolymerization. Oxygen-containing solvents (esters, ethers, ketones) tend to react with the halide and may nullify the desired effect. Other substances may be used as auxiliary dispersing or peptizing agents for depolymerizates which for some reason may show the tendency for gelation (too small amounts of halides used, insuflicient dilution, etc.), e.g.,

furfuryl alcohol, diacetone alcohol, carbinol, aniline, ace-' tone, ethyl ether, gylcol ethers, pyridine. However, such a peptization is not the same as the depolymerization by halides of S(Se, Te).

EXAMPLES The following examples show how the principles of the invention are applied in specific instances:

Example I.P0ly-sulfenyl-chloride of natural rubber To a solution of grams of pale crepe natural rub her in benzene (total volume 2000 ml.) is added a solution of grams of sulfur dichloride in benzene (total volume 800 mL). Though no precipitation occurs, the reaction is instantaneous, as can be seen from gelation times of smaller amounts of SCl Grams of S01, per 100 grams of rubber- 4 16 Gelation times in minutes 80 5 32 72 160 200 0. l 1 m on Example II.Ply-sulfenyl-chloride of butyl rubber To a solution of 100 grams of butyl rubber in sufficient toluene to give a total volume of 2000 ml., a solution of 16 grams of sulfur dichloride, in suflicient toluene to give a total volume of 80 ml. is added. The reaction is somewhat slower than with natural rubber, so that the end of the condensation is reached in approximately /2 hour; however, no thickening or gelation occurs, which is the case when mixtures with smaller amounts of sulfur chloride are reacted. The condensate, isolated e.g. by evaporation of the solvent, is very elastic, somewhat tacky and yields transparent glossy films.

Example IIl.P0ly-sulfenyl-chloride of cyclicized rubber To a solution of 100 grams of cyclicized rubber, for instance Pliolite SL 5, in suflicient aromatic solvent to give a total volume of 2000 ml., is added a solution of 120 grams of sulfur dichloride in an aromatic solvent (total volume 600 ml.). The rate of reaction is of the same order of magnitude as with pale crepe rubber. The depolymerizate, isolated for instance by evaporation of the solvent, yields hard, brittle, glossy films of reddish grey 'color.

Example lV.P0ly-sulfenyl-chloride of turpentine If to undiluted turpentine various amounts of a 20% sulfur chloride solution are added, a vivid reaction is observed but no gelation. However, the nature of the condensate, isolated for instance by evaporation of the solvent, indicates distinctly the presence of an inflection point, and places the state of depolymerization beyond approximately 128 grams per 100 grams of turpentine:

Grams of SCI; 8 64 128 256. Nature of the con- Light oil Heavy oil Wax Thick oil densate. creme. creme. yellow. bright yellow.

Example V.-P0ly-sulfenyl-clzloride of acetylacetone If undiluted acetylacetone is treated with various amounts of a 20% solution of SCl in an aromatic solvent 8 Example VI.-P0ly-sulfenyl-chl0ride of diacetone alcohol When undiluted diacetone alcohol is treated with various amounts of sulfur dichloride (e.g. a 20% solution in benzene), no gelation occurs. However, if by evaporation of the solvent e.g. at room temperature, the condensate is recovered, one finds a distinct point in its consistency, a maximum, beyond which lies the region of depolymerization. Approximately 500 grams of S01 per 100 grams of diacetone alcohol correspond to this optimum of condensation:

Grams of S01 per 100 grams 4 64 500 1,000

of diacetone alcohol. Properties of the condensate- Liquid Taeky Elastic Plastic.

dark viscous mass condensate Example VII.Poly-sulfenyl-clzloride f malonic ester Grams of S01 per 100 grams 2 16 32 64.

ethyl malonate. Nature of the condensate Hard film and un- Elastic Viscous changed condensate film. liquid.

Thus, in order to obtain poly-sulfenyl-chlorides of ethyl malonate, more than 32 gr. of SC1 per 100 grams of the ester are required.

Example VIII.-Poly-sulfenyl-clzl0ride of glycol A mixture of 64 grams sulfur (2 mols) with 136 grams of S Cl (1 mol) and 0.04 gram of iodine is heated, for instance, to boiling during 6 hours. The iodine acting as catalyst, the compound S Cl is formed. On addition of 31 grams glycol /2 mol) to this tetrasulfo-dichloride.

a greyish yellow waxy mass is formed, which can be washed for instance with naphta, benzene, acetone; if boiled with water, it yields a bright yellow plastic mass, insoluble in CS Example IX .Poly-sulfenyl-chloride of resorcinol By treating finely powdered resorcinol with various amounts of sulfur dichloride (for instance a 20% solution in toluene), and removing the solvent after some standing (for instance 36 hours), one produces condensates the general characteristic of which is a progressive approach toward a peak in consistency, after which depolymeriza-.

tion can be identified:

Grams of S01; per 100 grams resorcinol.

Characteristics of the condensates.

Resorein gran- Mainly red Red brown Mainly red Viscous red ules cemented brown plastic brown brown oil. by; conden- 011. mass. viilscous a e. o

Grams ofSChper 2 16 32 I 123,

100 gr. of acetylacetone. Properties of the Waxy, long Harder, less Resinous Cherry red,

condensate. crystals. dist. hard thick crystals. mass. 7 liquid.

Thus, using more than 32 grams of sulfur dichloride per 100 grams of acetylacetone, the poly-sulfenyl-chloride is obtained.

The proportion of SCl to be used in order to obtain polysulfenyl-chlorides of resorcinol is more than 32 grams per grams of the organic material. Example X .--Poly-sulfenyl-chl0ride of phenylene diamine 1,4 phenylene diamine is treated with various amounts of sulfur dichloride (for instance a 20% solution in benzene). After 24 hours standing the reaction products are treated with water giving:

Grams of SCI per 100 2 8 16 64.

grams phenylenediamine Properties of the condensate. Violet soluble in Grey plas- Brow water, some grey tic fuS- oil. plastic. ible to black tar.

Phenylene diamine being isoluble in benzene, the reaction takes place between small solid particles of the organic material and dissolved SCl it is consequently heterogenous. Using more than 16 grams of SCl per 100 grams 1o ments of the poly-sulfenyl-chloride and the reaction products were identified in separate phases.

Co-condensation opens avenues for the practical use of poly-sulfenyl-chlorides. For example, I was able to of Phenylene diamine: obtams poly'sulfenyl'chlondes- 5 develop poly-sulfenyl-chloride varnishes for rubber goods Example XI.Poly-sulfenyl-chloride of saccharose (natural and y Which are elastic, extremely Finely owdered suoar is treated with various amounts hesive, glossy and resistant to wear. Being colorless, they of, for instance, a 20 benzene solution of SCl The can be used even on pttsttfl Shade Stocks Requiring. no reaction is heterogenous since sugar is not soluble in heat treatment i drylttg .qulckly y cmmndentatlon benzene, and thorough mixing of the reagents is helpful. 10 they t be apphed by dlppmg brushmg or FPraymg, to After 24 hours standing and having evaporated the solvent, Vulcamzed other can be one obtains, besides somewhat caramelized (but otherused r bondmg both Pnvulcamzed a vulfiamzed wise unchanged) sugar, condensation products which show her artlcles- Here f P heatmg 1S Teqlmed and the an evolution towards a highly condensed elastic yellowish strength f the Seams 15 higher than the l'eslstanee 0f the mass, corresponding approximately to a proportion f material itself, even between heterogenous substances 100 grams of sugar to 16 grams of SCl The condensates l natural r S, -L et ey t transition Poiut are Y more less As mentioned above, treatment of drying oils with some vlscous 0115- 30% sulfur chloride produces substitute (Factice). This E l XII P0ly-Sulfenyl-chlgridg f urea latter is being used industrially as a plasticizer in rubber Finely powdered urea is treated with various amounts goods such. practlce ttlendmg oll'sulfurchlonde' of Sulfur dichloride (for example a 20% Solution in condensates with polyolefines s, however, no co-condensabenzene) and, after Standing for some 36 hours at room tron with poly-sulfenyl-chlorldes 1n termsof this mventemperature, by evaprating the Solvent, one obtains com tion. For such co-condensation the substitutes ought to densates showing clearly an evolution towards an inflec- Contaln Teactlve sulfuflse, p Whleh, If y tion point and a region of depolymerization, for quantities Were P would immediately eo-eendense With of more tha approximately 16 grams of SCI per 100 ber, scorching it on the rubber mill, rendering it hard grams of urea: and unutilizable, rather than plastic. This necessarily Grams of S012 per 100 grams 4 1 2 64.

Pr pe rti s of the condensate Urea grains Plastic Plastic with Viscous cemented by mass. viscous oil. yellow oil. condensate.

Example XIII.C0-condensates of poly-sulfenyl-urea applies to the Improved Facti'ce of Snelling (USP with various unsaturated substances 40 1,430,034).

A cold saturated water solution of 100 grams of urea In Summary the Process of t mventlon yletds is mixed with 660 grams of S Cl (prepared for instance stances Whose essenttal feature a degree t condenstt' by boiling for 6 hours of 212 grams of S Cl with 448 non beyond the mttxtmum .posstble for thc e organ: grams of elemental sulfur and 0.132 grams of elemental substance Accordmg to the cOnde.nsatton products iodine). After Standing for some time a bright yellow, of unsaturated compounds with the halides of the sulfur pasty mass is obtainedfamily pass physlcally through the stage of maximum Co-condensation of this urea-sulfenyl-chloride e.g. by cross-1111mm? a Stage chttractenzed by a lower degree boiling at atmospheric pressure with various unsaturated of potymenzatton'. t earned out to thgfuntst extent substances gives: With acetone a sticky mass; with metha depotyntenzatton ttstores the lmttat i of the anol a yellow somewhat plastic substance; with nonenes g t i t pnor to the crossllmkmg by a yellowish elastic condensate; with urea (saturated i j s oweget r not t z go so aqueous solution) a hard product; with water a light P s t came 0 any Pomt etween colored mass resistant to the action of solvents. These e .maxlmum crosstmkmg t the Complete depolymer' reactions were performed with the unsaturated comt t As to the actual .cqnslstency of the end'pmduct poncnts in excess of the stoichiometric requirements by tt from the ptasttctty of t t 0r.even t the poly-sulfenyl-chloride, the co-condensates being obe astlclty of raw t j t to the fimdtty t a mldtfle tained in separate phase as precipitates or immiscible depending on the initial state of the organic material. In 1iquids each instance, however, the depolymerized product will be less viscous, more plastic, lower melting, and more Example XIV.P0ly-sulfenyl-chloride of soybean oil and soluble, than at the point of maximum condensation co-condensates with various unsaturated substances which is obtained with smaller amounts of the halides of S(Se, Te).

Treatment of 50 grams of SOYbQaH O11 Wlth 100 grtflms Chemically, the compounds depolymerized by the proc- Of sulfur monochlonde PYOdPCeS mstantanemfls t ess of my invention are different from condensates partly tsfy ig g z g tgzg gi g g i fii f gggi igig rg or exhaustively cross-linked by S(Se, Te)halides. As hours) yielding a viscous black oil which can be kept in- Soon as.the amount P the latter exteeds V2 eqmvalent definitely. This poly sulfenyl chloride of Soybean Oil per equivalent of or1g1nal unsaturation, the completely acts as follows on mixing with unsaturated substances: crossdtmked condensates ctmespqnd to the formula: glycerol and glycol-ethyl-ether yield tacky co-condensates; 7 XNR (Z1I1) N RXN (m Whlch 15 a halogen; R an pyridine aleather-like substance; ammonia reacts suddenly orgamc radlcal; Te; m 13 2, 3 4; N 15 a to a dull brown mass; water and ethyl-alcohol yield elastic Whole number larger than (me), begin to p y i rubber-like substances of dull olive color. In this instance Unilatel'al'ly bound m groups Will pp in them, again the unsaturated components of co-condensation their number increasing with added m 2 until, in the were applied in amounts exceeding the saturation requirecase of complete depolymerization, all unsaturated groups where n is a whole number smaller than N.

Since all unsaturated groups of the organic molecule are consumed, the obtained depolymerizates are stable.

On the other hand, however, their principal chemical characteristic is the presence of highly reactive -Z X groups bound to R under elimination of only one X atom. This makes them of interest for numerous syntheses, one class of which is the co-condensation with compounds carrying unsaturated constituents. Such cocondensation yields structures as represented by formulas:

of the unsaturated molecules (R) and (R) with Z X since this latter results in mixtures of:

unfractionable due to high molecularity.

To those skilled in the art to which this invention relates, many changes in formulation and widely difiering embodiments and applications of the procedure will suggest themselves without departing from the spirit of my discovery and of its scope. The disclosure and the description herein are purely illustrative and are not intended to be in any sense limitative.

I claim:

1. A process for depolymerizing polymers which comprises:

(a) Reacting an organic monomer containing at least two unsaturated constituents, said monomer being selected from the group consisting of ethylenically unsaturated organic monomers, acetylenically unsaturated organic monomers, organic monomers containing unsaturated oxygen linkages and organic monomers containing unsaturated nitrogen linkages with exactly one half equivalent per equivalent of monomeric unsaturation of a member selected from the group consisting of sulfur halides, selenium ha lides, and tellurium halides to form an exhaustively cross-linked polymer.

(b) Depolymerizing said exhaustively cross-linked polymer by further reaction with additional quantities of said halides beyond the requirements for exhaustive cross-linking to produce by the splitting of said cross-links unilaterally bound highly reactive halide side chains. 2. The process of claim 1 in which the reactive side chains consist of sulfur halides.

3. The process of claim 1 in which the reactive side chains consist of sulfur chloride.

4. The process of claim 1 in which the organic monomers contain ethylenically unsaturated double bonds.

5. The process of claim 1 in which the organic monomers contain acetyleni-cally unsaturated linkages.

6. The process of claim 1 in which the organic monomers contain unsaturated oxygen linkages.

7. The process of claim 1 in which the organic monomer contains unsaturated nitrogen links.

8. The process of claim 1 in which the required amount of halide for both steps (a) and (b) is added in one portion.

9. The process of claim 1 in which the required amount of halide for both steps (a) and (b) is added in several fractional portions.

10. The process of claim 1 carried out in the presence of an inert organic solvent.

11. The process of claim 1 carried out in the presence of an inert aromatic solvent.

7 12. The process of claim 1 carried out in the of an inert aliphatic solvent.

13. The process of claim 1 carried out in the presence of an inert hydrogenated solvent.

14. The process of claim 1 carried out in the presence of an inert halogenated solvent.

15. The process of claim 1 carried out in the absence of solvents.

presence References Cited by the Examiner UNITED STATES PATENTS 1,978,829 10/1934 Gray 2601 2,114,314 5/1938 Patrick 260-79 2,152,828 4/1939 Thomas 26094 OTHER REFERENCES Rubber Age, Volume 83, September 1958, TS 1870 R6 

1. A PROCESS FOR DEPOLYMERIZING POLYMERS WHICH COMPRISES: (A) REACTING AN ORGANIC MONOMER CONTAINING AT LEAST TWO UNSATURATED CONSTITUENTS, SAID MONOMER BEING SELECTED FROM THE GROUP CONSISTING OF ETHYLENICALLY UNSATURATED ORGANIC MONOMERS, ACETYLENICALLY UNSATURATED ORGANIC MONOMERS, ORGANIC MONOMERS CONTAINING UNSATURATED OXYGEN LINKAGES AD ORGANIC MONOMERS CONTAINING UNSATURATED NITROGEN LINKAGES WITH EXACTLY ONE HALF EQUIVALENT PER EQUIVALENT OF MONOMERIC UNSATURATION OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF SULFUR HALIDES, SELENIUM HALIDES, AND TELLURIUM HALIDES TO FORM AN EXHAUSTIVELY CROSS-LINKED POLYMER. (B) DEPOLYMERIZING SAID EXHAUSTIVELY CROSS-LINKED POLYMER BY FURTHER REACTION WITH ADDITIONAL QUANTITIES OF SAID HALIDES BEYOND THE REQUIREMENTS FOR EXHAUSTIVE CROSS-LINKING TO PRODUCE BY THE SPLITTING OF SAID CROSS-LINKS UNILATERALLY BOUND HIGHLY REACTIVE HALIDE SIDE CHAINS. 